發(fā)布時間：2018-04-25 22:26

  本文選題：氯甲基化 + 季銨化��； 參考：《東華大學(xué)》2017年碩士論文

【摘要】：小劑量的內(nèi)毒素就能夠引起廣泛的生理病理反應(yīng),如機體發(fā)熱、白細胞反應(yīng)、糖代謝紊亂、血管舒縮機制紊亂等,嚴(yán)重者可導(dǎo)致死亡。內(nèi)毒素廣泛存在于各種環(huán)境中,因此,在醫(yī)用領(lǐng)域中(如:醫(yī)用過濾裝置),亟待尋找一種高效去除內(nèi)毒素、適合大批量工業(yè)生產(chǎn)的方法。本課題針對國內(nèi)外內(nèi)毒素的濾除情況做了大量的調(diào)查研究,尋找了一種高效去除內(nèi)毒素的方法,將特異性去除內(nèi)毒素方法—陰離子交換法和非特異性去除內(nèi)毒素方法—過濾法進行結(jié)合,探究其內(nèi)毒素去除效果。本課題選用制膜普遍采用的聚醚砜,先進行氯甲基化反應(yīng)、再進行季銨化反應(yīng),希望得到聚醚砜陰離子內(nèi)毒素過濾膜。本課題首先選擇在聚醚砜的側(cè)鏈上引入氯甲基基團(-CH_2Cl)作為反應(yīng)跳板,尋找了反應(yīng)活性高、反應(yīng)時間短、反應(yīng)效果好、環(huán)境友好的1、4-二氯甲氧基丁烷作為氯甲基化反應(yīng)的試劑,路易斯酸-氯化鋅作為反應(yīng)催化劑。并設(shè)計三因子三水平正交試驗來比較聚醚砜氯甲基化反應(yīng)中反應(yīng)時間、反應(yīng)溫度、氯甲基化試劑用量對聚醚砜氯甲基化程度的影響,通過核磁共振圖譜來表征其氯甲基化程度,實驗結(jié)果發(fā)現(xiàn)聚醚砜氯甲基化程度隨著反應(yīng)溫度的升高而升高,最優(yōu)的反應(yīng)溫度為90度;隨著氯甲基化試劑用量的增多也隨之變高,最優(yōu)的氯甲基化試劑用量為14.4g;隨著反應(yīng)時間的增加,反應(yīng)速度由快變慢,最佳的反應(yīng)時間為6h。隨后選取氯甲基化程度最高的聚醚砜作為反應(yīng)物進行聚醚砜季銨化反應(yīng)。聚醚砜的季銨化是以三級銨R3N和鹵代烷R-X為反應(yīng)物,生成季銨鹽[R_4N~+][X-]的反應(yīng)。選取反應(yīng)活性高的三甲胺作為季銨化試劑,常溫反應(yīng)制備聚醚砜陰離子內(nèi)毒素過濾膜。通過化學(xué)手段表征,紅外光譜圖顯示聚醚砜陰離子內(nèi)毒素過濾膜表面有季銨基團的特征峰;zeta電位顯示聚醚砜陰離子內(nèi)毒素過濾膜表面帶有正電荷,與季銨基團為強堿性基團,在水中顯示正電性理論相符。通過物理手段表征,接觸角顯示聚醚砜陰離子內(nèi)毒素過濾膜接觸角變小,親水性變好,與季銨基團為親水性基團理論相符;電鏡結(jié)果顯示,氯甲基化聚醚砜膜表面在進行季銨化反應(yīng)之后變得坑洼;阻水透氣性能顯示,由于反應(yīng)過程中基布纖維的溶脹,使得相比較氯甲基化的聚醚砜,季銨化聚醚砜透氣性能稍變差,阻水性能稍變好。本課題進一步選用0.25EU/ml靈敏度的鱟試劑進行內(nèi)毒素檢驗,根據(jù)鱟試劑與內(nèi)毒素反應(yīng)產(chǎn)生凝膠的原理,通過翻轉(zhuǎn)試管觀察凝膠的形態(tài)來判斷結(jié)果,發(fā)現(xiàn)通過聚醚砜陰離子內(nèi)毒素過濾膜濾除前的溶液為凝膠態(tài),濾除后溶液為液態(tài),進一步顯示聚醚砜陰離子內(nèi)毒素過濾膜能夠成功濾除內(nèi)毒素。綜上所述,通過以1、4-二氯甲氧基丁烷為氯甲基化試劑在反應(yīng)溫度為90度,反應(yīng)時間為6h,氯甲基化試劑為14.4g時成功制備氯甲基化聚醚砜程度最高;以三甲胺為季銨化試劑常溫反應(yīng)15天,能夠成功制備聚醚砜陰離子內(nèi)毒素過濾膜并能有效濾除內(nèi)毒素。
[Abstract]:A small dose of endotoxin can cause a wide range of physiological and pathological reactions, such as body fever, leukocyte reaction, disorder of sugar metabolism, and disorder of vasoconstriction, and so on. Serious people can cause death. Endotoxin is widely found in various environments. Therefore, in medical field (such as medical filter device), it is urgent to find a kind of efficient endotoxin removal. In accordance with the method of mass production in large quantities, this subject has done a lot of investigations and studies on the filtration of endotoxin at home and abroad, and found a method of efficient removal of endotoxin. It combines the specific removal of endotoxin method and the nonspecific removal endotoxin method - filtration method to explore the effect of endotoxin removal. This topic selects the Polyethersulfone anionic endotoxin ultrafiltration membrane. The first choice is to introduce the chloromethyl group (-CH_2Cl) on the side chain of polyethersulfone as the reaction springboard, and find the reaction activity is high, the reaction time is short, and the reaction effect is found. Good, environmentally friendly 1,4- two chloromethyl butane as a reagent for chloromethylation, Lewis acid and zinc chloride as a reaction catalyst. And a three factor three level orthogonal test was designed to compare the reaction time, reaction temperature, and the effect of the amount of chloromethylation reagents on the degree of chloromethylation of polyethersulfone. The results show that the degree of chloromethylation of polyethersulfone increases with the increase of reaction temperature, and the optimum reaction temperature is 90 degrees. With the increase of the amount of chloromethylation reagents, the optimal dosage of chloromethylation reagents is 14.4g. With the increase of reaction time, the reaction speed is increased. The optimum reaction time is 6h. and then the Polyethersulfone is then selected as the reactant with the highest chloromethylated polyethersulfone as the reactant. The quaternatization of polyethersulfone is based on the reaction of three ammonium R3N and halogenated R-X to produce quaternary ammonium salt [R_4N~+][X-]. The Polyethersulfone anionic endotoxin membrane should be prepared. By chemical means, the infrared spectrum shows the characteristic peak of the quaternary ammonium group on the surface of the Polyethersulfone anionic endotoxin membrane, and the zeta potential shows that the surface of the Polyethersulfone anionic endotoxin membrane has positive charge, and the Ji Anji group is a strong basic group, and the positive electricity is displayed in the water. According to the physical means, the contact angle shows that the contact angle of the Polyethersulfone anionic endotoxin membrane is smaller, the hydrophilicity is better and the quaternary ammonium group is the hydrophilic group theory; the electron microscope results show that the surface of the chloromethyl polyethersulfone membrane becomes potholed after the quaternizing reaction; the water resistance and permeability performance shows, the reaction process is due to the reaction process. The swelling of the medium fabric fiber makes the Polyethersulfone with chloromethylation, and the permeability of quaternated polyethersulfone is slightly worse, and the water resistance performance is slightly better. This subject further selects the endotoxin test by the 0.25EU/ml sensitivity limulus reagent. According to the principle of condensing of the limulus reagent and the endotoxin reaction, the morphology of the gel is observed by the reversal test tube. To determine the results, it is found that the solution of the filtration membrane of the Polyethersulfone anionic endotoxin filter membrane is a gelation state and the filtrate is filtrated into liquid, which further shows that the Polyethersulfone anionic endotoxin filter membrane can successfully filter the endotoxin. In summary, the reaction temperature is 90 degrees by the reaction temperature of 1,4- two chloromethyl butane as the chloromethylated reagent. The successful preparation of chloromethylated polyethersulfone at the time of 6h and chloromethylation of 14.4g is the highest. With trimethylamine as a quaternated reagent at normal temperature for 15 days, the Polyethersulfone anionic endotoxin filter membrane can be successfully prepared and the endotoxin can be effectively filtered out.

【學(xué)位授予單位】：東華大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ051.893

【參考文獻】

相關(guān)期刊論文 前10條

1 顧梁;孫哲;徐丹;嚴(yán)鋒;;堿性陰離子交換聚合物膜研究進展[J];功能高分子學(xué)報;2016年02期

2 徐建新;王松濤;楊海軍;聶雪川;趙璨;仵峰;侯錚遲;;我國聚醚砜超濾膜的研發(fā)進展綜述[J];凈水技術(shù);2016年03期

3 陳榮;李昂;房世超;畢慧平;胡朝霞;陳守文;;自交聯(lián)型季銨化聚醚砜陰離子交換膜的制備與性能[J];高分子學(xué)報;2016年04期

4 胡蒙蒙;吳雪梅;焉曉明;賀高紅;張瑩;方達暉;孫園園;;三甲胺聚砜氫氧根離子交換膜的均相法制備與性能[J];高分子材料科學(xué)與工程;2015年08期

5 馬瑩博;;生物制劑中內(nèi)毒素去除方法概述[J];河北企業(yè);2015年04期

6 戴思思;徐業(yè);趙俊;盧冰;何立群;;聚醚砜膜透析器對腎纖維化終末期血透患者血清β_2微球蛋白清除作用的研究[J];中國醫(yī)學(xué)裝備;2015年03期

7 徐業(yè);戴思思;趙俊;盧冰;沈曉琴;王力勇;黃科;何立群;;不同透析膜在腎纖維化患者血液透析中對血清β_2MG、iPTH和hs-CRP的影響[J];中國醫(yī)學(xué)裝備;2015年02期

8 劉艷;林峰;張海欣;蔡木易;;超濾法去除食源性低聚肽中的細菌內(nèi)毒素[J];食品科技;2014年12期

9 褚小立;陸婉珍;;近五年我國近紅外光譜分析技術(shù)研究與應(yīng)用進展[J];光譜學(xué)與光譜分析;2014年10期

10 張瑩;吳雪梅;賀高紅;焉曉明;張彥普;王俊俊;;咪唑季銨化聚醚砜陰離子交換膜的制備與性能表征[J];高分子材料科學(xué)與工程;2014年06期

相關(guān)會議論文 前1條

1 孫海翔;張林;柴紅;陳歡林;;殼聚糖親和膜脫除蛋白質(zhì)溶液中內(nèi)毒素的研究[A];第一屆全國化學(xué)工程與生物化工年會論文摘要集(上)[C];2004年

相關(guān)博士學(xué)位論文 前1條

1 申利國;聚醚砜（PES）膜改性及抗污染性能研究[D];中國科學(xué)院研究生院（上海應(yīng)用物理研究所）;2014年

相關(guān)碩士學(xué)位論文 前6條

1 楊堤;噻唑和吡咯烷季銨化氫氧根離子交換膜的制備及性能[D];大連理工大學(xué);2015年

2 黃湛;季銨化聚醚砜CO_2固定載體分離膜的研究[D];大連理工大學(xué);2014年

3 張國振;聚芳醚砜耐溶劑納濾膜的研制[D];大連理工大學(xué);2014年

4 楊婉;聚醚砜荷電膜的制備與性能研究[D];西安建筑科技大學(xué);2014年

5 黃冬冬;聚醚砜的功能化改性及其膜的性能研究[D];浙江工業(yè)大學(xué);2014年

6 徐X;聚偏氟乙烯接枝氨基酸親和膜及其內(nèi)毒素脫除研究[D];浙江大學(xué);2010年

，

本文編號：1803268